EP0548617B1 - Carburants pour moteurs à allumage par étincelle - Google Patents

Carburants pour moteurs à allumage par étincelle Download PDF

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EP0548617B1
EP0548617B1 EP92120622A EP92120622A EP0548617B1 EP 0548617 B1 EP0548617 B1 EP 0548617B1 EP 92120622 A EP92120622 A EP 92120622A EP 92120622 A EP92120622 A EP 92120622A EP 0548617 B1 EP0548617 B1 EP 0548617B1
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Prior art keywords
fuel
fuels
weight
detergent component
additives
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German (de)
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EP0548617A3 (fr
EP0548617A2 (fr
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Jürgen Dr. Mohr
Knut Dr. Oppenländer
Jürgen Dr. Thomas
Peter Dr. Schreyer
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
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    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Definitions

  • the invention relates to fuels for gasoline engines which contain small amounts of a combination of a nitrogen-containing detergent component and a carrier oil component, the carrier oil component comprising dialkylphenol-started propoxylates.
  • Carburetor and intake system of gasoline engines are increasingly contaminated by contaminants that are caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase ventilation gases passed into the carburetor.
  • the first generation of additives could only prevent the formation of deposits in the intake system, but not remove existing deposits, whereas the modern additives of the second generation can do both ("keep-clean” and "clean-up effect") and because of changed thermal properties, in particular also at zones of higher temperatures, namely at the inlet valves.
  • carrier oils in particular play a central role here.
  • the addition of carrier oil can have a positive effect on engine areas which are normally not reached by the conventional additives, which mainly act in the intake system.
  • US Pat. No. 4,877,416 discloses fuel mixtures which, in addition to an amine as detergent component, contain a carrier oil.
  • a carrier oil Poly (oxyalkylene) monools with hydrocarbon end groups are mentioned as carrier oil.
  • a large number of possible radicals are mentioned as hydrocarbon end groups, including in particular C7-C30-alkylphenyl.
  • a carrier oil is described which was obtained by butoxylation of dodecylphenol.
  • the compatibility with one another must also be taken into account when selecting additives.
  • the detergents and carrier oils if present in a concentrate, must not lead to deposition or phase separation. This is according to US 4,877,416 for the alkylphenol-started carrier oils e.g. achieved in that butylene oxide is used as the alkylene oxide, which, however, is relatively expensive to produce and its use is cost-intensive.
  • the alkoxylates according to the invention although no butylene oxide is used for their preparation, have good compatibility with the nitrogen-containing detergent component and also prevent the deposits mentioned in the inlet system and in the combustion chamber.
  • the alkoxylates of the formula I according to the invention also provide compatibility with the detergent when a monoalkyl-substituted propoxylate is present as an additional component of the carrier oil component, although this propoxylate is not readily compatible with the Nitrogen-containing detergent component is compatible.
  • the carrier oil component can therefore also comprise 10 to 5000 ppm (based on the fuel) of a monoalkylphenol-started propoxylate, the structure given in formula I applying to this propoxylate, with the proviso that R 1 is omitted, and in particular, the amount of the monoalkylphenol started propoxylate is not greater than the amount of the dialkylphenol started propoxylate according to formula I.
  • the fuels preferably contain 20 to 2,000 ppm, in particular 50 to 1,000 ppm (all ppm data are in each case based on the weight) of the detergent component a) or of the alkoxylate b).
  • nitrogen-containing detergent component in the mixture with the carrier oils according to the invention it is possible in principle to use any known of the products suitable for this purpose, such as those e.g. with J. Falbe, U. Hasserodt, catalysts, surfactants and mineral oil additives, G. Thieme Verlag Stuttgart 1978, p. 221 f. or in K. Owen, Gasoline and Diesel Fuel Additives, John Wiley & Sons 1989, pp. 23 ff.
  • Amides or imides of polyisobutylene succinic anhydride, polybutene polyamines and long-chain carbonamides and imides are suitable as further detergents or additional dispersants.
  • dialkylphenols used as starters are prepared in a customary manner by Friedel-Crafts alkylation of phenols with the corresponding olefins or olefin mixtures.
  • the propoxylates according to the invention have excellent compatibility, particularly with the polyisobutylamines already mentioned in the respective formulations.
  • Leaded and especially unleaded regular and premium gasoline are considered as fuels for gasoline engines.
  • the gasolines can also contain components other than hydrocarbons, e.g. Alcohols for methanol, ethanol, tert-butanol and ethers, e.g. Contain methyl tertiary butyl ether.
  • the fuels generally also contain further additives such as corrosion inhibitors, stabilizers, antioxidants and / or further detergents.
  • Corrosion inhibitors are mostly ammonium salts org. Carboxylic acids which tend to form films due to the corresponding structure of the starting compounds. Amines to lower the pH are also often found in corrosion inhibitors. Heterocyclic aromatics are mostly used as non-ferrous metal corrosion protection.
  • Antioxidants or stabilizers include, in particular, amines such as para-phenylenediamine, dicyclohexylamine, morpholine or derivatives of these amines.
  • Phenolic antioxidants such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxiphenylpropionic acid and their derivatives are also added to fuels and lubricants.
  • thermogravimetric analyzes as a measure of the effectiveness with regard to combustion chamber deposits, since a general engine test for this does not yet exist.
  • thermogravimetric analyzes provide information about the thermal load capacity of a sample, eg a thermo-oxidative condition.
  • thermo-oxidative condition e.g. a thermo-oxidative condition.
  • they allow conclusions to be drawn about the formation of deposits or residual amounts after such a thermo-oxidative treatment.
  • the high thermal load-bearing capacity combined with the least possible to vanishing residue formation is favorable for use as carrier oil in the sense of this invention.
  • alkoxylates of longer-chain dialkylphenols according to the invention meet all of these requirements (synergism with detergents, demonstrated in the engine test; excellent thermooxidative properties, verified by thermogravimetric analysis) to a high degree.
  • the additive combination of nitrogen-containing detergent component and alkoxylate as carrier oil component is preferably provided as a concentrate which contains 10 to 80% by weight, in particular 30 to 60% by weight, of the detergent component and 5 to 70% by weight .-%, in particular 20 to 60 wt .-% of the carrier oil component, ie of the propoxylate.
  • the concentrate contains a suitable solvent, e.g. aromatic and / or aliphatic hydrocarbons, especially heavy naphtha (Solvesso®).
  • thermogravimetry curve shown in the figure shows the relative mass decrease m / m o as a function of the temperature at a heating rate of 2 ° C. per minute and in the presence of air.
  • the half-life temperature of 260 to 270 ° C indicates sufficient thermo-oxidative stability; at higher temperatures the product disintegrates almost without residue (m is the mass measured in each case, m o the initial mass).

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Claims (6)

  1. Carburants pour moteurs à allumage par étincelles, contenant une combinaison de
    a) 10 à 5.000 ppm d'un composant de détergence contenant de l'azote et
    b) 10 à 5.0000 ppm d'un alcoolate de la formule I
    Figure imgb0005
     dans laquelle
    R¹ et R   représentent chacun indépendamment l'un de l'autre, un radical alkyle en C₆ à C₃₀ ramifié ou non ramifié,
    l'un des deux symboles R³ représente le radical méthyle cependant que l'autre représente un atome d'hydrogène et
    n =   1 à 100.
  2. Carburants suivant la revendication 1, caractérisés en ce que le composant de détergence a) est au moins un composé avec un radical amine, amide, ou imide.
  3. Carburants suivant la revendication 2, caractérisés en ce que le composant de détergence a) est ou contient une polyisobutylamine.
  4. Carburants suivant la revendication 1, caractérisés en ce que R¹ et/ou R représentent chacun un radical alkyle en C₇ à C₁₈ ramifié ou non ramifié.
  5. Carburants suivant la revendication 1, caractérisés en ce que n = 5 à 50, plus particulièrement 7 à 30.
  6. Concentré des composants a) et b) suivant la revendication 1 dans un solvant, contenant 10 à 80% en poids du composant de détergence contenant de l'azote a) et 5 à 70% en poids de l'alcoolate b) de la formule I, ainsi qu'un solvant en une proportion nécessaire pour compléter le concentré jusqu'à 100% en poids.
EP92120622A 1991-12-20 1992-12-03 Carburants pour moteurs à allumage par étincelle Expired - Lifetime EP0548617B1 (fr)

Applications Claiming Priority (2)

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DE4142241 1991-12-20
DE4142241A DE4142241A1 (de) 1991-12-20 1991-12-20 Kraftstoffe fuer ottomotoren

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EP0548617A2 EP0548617A2 (fr) 1993-06-30
EP0548617A3 EP0548617A3 (fr) 1993-07-21
EP0548617B1 true EP0548617B1 (fr) 1996-03-13

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US8814957B2 (en) 2004-08-05 2014-08-26 Basf Aktiengesellschaft Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion

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CA2082435C (fr) 2000-11-07
EP0548617A3 (fr) 1993-07-21
EP0548617A2 (fr) 1993-06-30
DE4142241A1 (de) 1993-06-24
US5298039A (en) 1994-03-29
CA2082435A1 (fr) 1993-06-21
DE59205692D1 (de) 1996-04-18
ES2084255T3 (es) 1996-05-01
ATE135394T1 (de) 1996-03-15

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